Theoretical analysis of electronic delocalization

A block-localized wave function method is introduced to evaluate the electronic delocalization effect in molecules. The wave function for the hypothetical and strictly localized structure is constructed based on the assumption that all electrons and primitive basis functions can be divided into several subgroups; each localized molecular orbital is expanded in terms of primitive orbitals belonging to only one subgroup. The molecular orbitals belonging to the same subgroup are constrained to be mutually orthogonal, while those belonging to different subgroups are free to overlap. The final block-localized wave function at the Hartree–Fock level is expressed by a Slater determinant. In this manner, the energy difference between the Hartree–Fock wave function and the block-localized wave function can be generally defined as the electronic delocalization energy. The method is applied to two cases. The first concerns the resonance stabilization in the allyl ions. We find that the vertical resonance energies fo...

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